Group iii nitride crystal and manufacturing method thereof

ABSTRACT

A group III nitride crystal containing therein an alkali metal element comprises a base body, a first group III nitride crystal formed such that at least a part thereof makes a contact with the base body, the first group III nitride crystal deflecting threading dislocations in a direction different from a direction of crystal growth from the base body and a second nitride crystal formed adjacent to the first group III nitride crystal, the second nitride crystal having a crystal growth surface generally perpendicular to the direction of the crystal growth.

TECHNICAL FIELD

The present invention relates to group III nitride crystals andmanufacturing method thereof.

These days, most of the InGaAlN (a group III nitride semiconductor)devices used for ultraviolet, purple, blue and green optical sources areformed on a substrate of sapphire or silicon carbide (SiC) by conductingthereon an MOCVD process (metal-organic chemical vapor depositionprocess) or MBE process (molecular beam epitaxy process).

In the case sapphire or silicon carbide is used for the substrate,however, there are formed a large number of crystal defects in the groupIII nitride semiconductor layers grown thereon in view of the fact thatthere exists a large difference in the thermal expansion coefficient andlattice constant between the substrate and the group III nitridesemiconductor layers. Such crystal defects invite deterioration ofdevice performance and are related directly to the drawbacks such asshort lifetime, large operational power, and the like, in the case alight-emitting device is formed on such a substrate.

Further, because a sapphire substrate is an insulator, it is impossibleto provide an electrode directly on the substrate contrary toconventional light-emitting devices. This means that it is necessary toprovide an electrode on one of the group III nitride semiconductorlayers. However, such a construction necessitates large device area forformation of the electrodes and the cost of the device is increasedinevitably. In addition, there is caused a problem of warp of thesubstrate because of combination of different materials such as use of asapphire substrate in combination with a group III nitride semiconductorlayer. This problem of warp becomes a serious problem particularly whenthe device area is increased.

Further, with the group III nitride semiconductor devices constructed ona sapphire substrate, chip separation by way of cleaving process isdifficult, and it is not easy to obtain an optical cavity edge surface,which is required in laser diodes (LD). Because of this, it has beenpracticed in-the art, when to form an optical cavity edge surface, toconduct a separation process somewhat similar to a cleaving processafter reducing the thickness of the sapphire substrate to 100 μm or lessby conducting polishing process, or by conducting a dry etching process.Thus, it has been difficult to conduct formation of optical cavity edgesurface and chip separation with a single step, contrary to theproduction process of conventional laser diodes, and there has been aproblem of increased cost because of the complexity of the fabricationprocess of light-emitting devices.

In order to solve these problems, there has been made a proposal forreducing the crystal defects by conducting selective growth process ofthe group III nitride semiconductor layers on the sapphire substrate ina lateral direction. With this approach, it has become possible toreduce the crystal defects successfully, while there still remainproblems of insulating nature of the sapphire substrate and difficultyof cleaving a sapphire substrate with such a construction.

In order to solve these problems, use of a gallium nitride (GaN)substrate of generally the same composition to the crystalline materialsgrown thereon is preferable. Thus, various attempts have been made forgrowing a bulk GaN crystal by vapor phase growth process or melt growthprocess. However, GaN substrate of high quality and practical size isnot yet realized.

As one approach of realizing a GaN bulk crystal substrate, there isproposed a GaN crystal growth process that uses sodium (Na) for the flux(Patent Reference 1). According to this method, sodium azide (NaN₃) andmetal Ga are confined in a reaction vessel of stainless steel (vesseldimension: inner diameter=7.5 mm; length=100 mm) as the source material,together with a nitrogen gas, and a GaN crystal is grown by holding thereaction vessel at a temperature of 600-800° C. for 24-100 hours.

According to this method, it has become possible to carry out thecrystal growth at relatively low temperature of 600-800° C. whilemaintaining the pressure inside the vessel to a relatively low pressureof 100 kg/cm² or less. This means that crystal growth can be conductedunder a practical condition.

Further, there is realized a high quality group III nitride crystal bycausing a reaction between a group V source material including nitrogenand a melt mixture of an alkali metal and a group III metal (PatentReference 2).

-   Patent Reference 1 U.S. Pat. No. 5,868,837-   Patent Reference 2 Japanese Laid-Open Patent Application 2001-58900

DISCLOSURE OF THE INVENTION

In the case of growing a group III nitride crystal on a base body byreacting a melt mixture of alkali metal and group III metal with a groupV source material including nitrogen, on the other hand, there arises aproblem, when the base body contains dislocations, in that there occurscrystal growth of a group III nitride that reflects such dislocations ofthe underlying base body. Therefore, it is difficult to reduce thedislocation density with the group III nitride crystal thus grown.

The present invention has been made in view of the foregoing problemsand has its object of providing a group III nitride crystal grown by acrystal growth process that uses alkali metal for a flux while reducingthreading dislocations.

Another object of the present invention is to provide a manufacturingmethod of a group III nitride crystal that uses an alkali metal for fluxwhile reducing threading dislocations.

According to the present invention, the group III nitride crystalcontains an alkali metal element as an impurity and includes a base bodyand first and second group III nitride crystals. The first group IIInitride crystal is formed such that at least a part thereof makes acontact with the base body and deflects threading dislocations in adirection different from a direction of crystal growth from the basebody. The second nitride crystal is formed adjacent to the first groupIII nitride crystal and has a crystal growth surface generallyperpendicular to the direction of the crystal growth.

In a preferred embodiment, the first group III nitride crystal has acrystal growth surface different from a c-surface or a plane parallel toa c-axis.

In a preferred embodiment, the second group III nitride crystal has acrystal growth direction in the c-axis direction.

In a preferred embodiment, the underlying body is a substrate of amaterial different from a material of the group III nitride crystal.

In a preferred embodiment, the base body comprises a substrate and athird group III nitride crystal. The substrate comprises a materialdifferent from a material of the group III nitride crystal. The thirdgroup III nitride crystal is formed on the substrate and includesthreading dislocations. Further, at least a part of the first nitridecrystal is formed adjacent to the third nitride crystal.

In a preferred embodiment, the third group III nitride is formed ofplural crystals disposed with a predetermined interval.

In a preferred embodiment, the predetermined interval is determined by asize of a semiconductor device formed by using the second group IIInitride.

In a preferred embodiment, the base body comprises a group III nitridecrystal.

In a preferred embodiment, the base body comprises a seed crystal and athird group III nitride crystal. The seed crystal comprises a group IIInitride crystal. The third group III nitride crystal is formed adjacentto the seed crystal and includes threading dislocations. Further, atleast a part of the first nitride crystal is formed adjacent to thethird nitride crystal.

In a preferred embodiment, the third group III nitride crystal has athreading dislocation density of 10⁶-10¹⁰ cm⁻².

Further, the present invention provides a manufacturing method formanufacturing a group III nitride crystal on a base body by using acrystal growth apparatus including a reaction vessel holding a meltmixture containing therein an alkali metal and a group III metal, themethod comprising: a first step of loading an alkali metal and a groupIII nitride into a reaction vessel in an ambient of an inert gas or anitrogen gas; a second step of filling a vessel space in the reactionvessel with a nitrogen gas; a third step of heating the reaction vesselto a crystal growth temperature; a fourth step of growing a first groupIII nitride crystal on the base body, such that the first group IIInitride crystal causes deflection of threading dislocations in adirection different from a crystal growth direction from the base body;a fifth step of growing a second group III nitride crystal having acrystal growth surface generally perpendicular to a crystal growthdirection such that at least of a part of the second group III nitridecrystal makes a contact with the first group III nitride crystal; and asixth step of supplying a nitrogen source gas to the reaction vesselsuch that a pressure of the vessel space is held at a predeterminedpressure.

In a preferred embodiment, the fourth step causes crystal growth of thefirst group III nitride crystal such that the first group III nitridecrystal has a crystal growth surface different from a c-surface or aplane parallel to a c-axis.

In a preferred embodiment, the fourth step causes crystal growth of thefirst group III nitride crystal by controlling the mixing ratio of thealkali metal and the group III metal and the nitrogen source gaspressure in the vessel space within the range of crystal growthcondition in which there occurs no new nucleation in the melt mixture.

In a preferred embodiment, the fourth step causes the crystal growth ofthe first group III nitride crystal by relatively lowering the nitrogensource gas pressure when the mixing ratio is relatively large and causesthe crystal growth of the first group III nitride by relativelyincreasing the nitrogen source gas pressure when the mixing ratio isrelatively small.

In a preferred embodiment, the fifth step causes crystal growth of thesecond group III nitride crystal by adding an additive different fromthe alkali metal or the group III metal to the melt mixture.

In a preferred embodiment, the fifth step causes the crystal growth ofthe second group III nitride crystal by adding the additive to the meltmixture under the crystal growth condition for growing the first groupIII nitride crystal.

In a preferred embodiment, the alkali metal comprises sodium, the groupIII metal comprises gallium, and the additive comprises lithium.

In a preferred embodiment, the lithium is used in the melt mixture ofsodium and gallium with a concentration of 0.5-0.8 mol.

In a preferred embodiment, the manufacturing method further comprises aseventh step of dipping the base body to the melt mixture.

In a preferred embodiment, the manufacturing method further comprises aseventh step of contacting the base body to the vapor-liquid interfacebetween the melt mixture and the vessel space.

In a preferred embodiment, the manufacturing method further comprises aneighth step of moving the base body with the growth of the first andsecond group III nitride crystal such that the crystal growth surfacemakes contact with the vapor-liquid interface.

In a preferred embodiment, the underlying body is a substrate of amaterial different from a material of the group III nitride crystal.

In a preferred embodiment, the base body comprises a substrate and athird group III nitride crystal. The substrate comprises a materialdifferent from a material of the group III nitride crystal. The thirdgroup III nitride crystal is formed on the substrate and includesthreading dislocations. Further, the fourth step causes the crystalgrowth of the first group III nitride crystal in contact with the thirdgroup III nitride crystal.

In a preferred embodiment, third group III nitride is formed of pluralcrystals each having a predetermined width and disposed with apredetermined interval.

In a preferred embodiment, the base body comprises a low-grade seedcrystal of the group III nitride and contains threading dislocations.

In a preferred embodiment, the base body comprises a seed crystal and athird group III nitride crystal. The seed crystal comprises a group IIInitride crystal. The third group III nitride crystal is formed adjacentto the seed crystal and includes threading dislocations. Further, thefourth step causes the crystal growth of the first group III nitridecrystal in contact with the third group III nitride crystal.

According to the present invention, a group III nitride crystalcontaining therein an alkali metal is manufactured by consecutivelycausing crystal growth processes of the first group III nitride crystalthat deflects the threading dislocations in the direction different fromthe direction of crystal growth from the base body, and the second groupIII nitride crystal having a crystal growth surface generallyperpendicular to the crystal growth direction of the first group IIInitride crystal. As a result, the threading dislocations penetratinginto the second group III nitride crystal is reduced.

Thus, according to the present invention, it becomes possible todecrease the threading dislocations in the group III nitride crystal.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional diagram showing the constructionof a crystal growth apparatus according to Embodiment 1 of the presentinvention;

FIG. 2 is an oblique view diagram showing the construction of astopper/inlet plug shown in FIG. 1;

FIG. 3 is a plan view diagram showing the state of mounting thestopper/inlet plug to a conduit;

FIG. 4 is a schematic diagram showing the relationship between thenitrogen gas pressure and the crystal growth temperature for the case ofgrowing a GaN crystal;

FIG. 5 is a diagram showing the relationship between the mole ratio ofmetal Na and metal Ga and the nitrogen gas pressure;

FIG. 6 is a schematic diagram showing the construction of a base bodyshown in FIG. 1;

FIGS. 7A-7F are diagrams showing the process steps for causing crystalgrowth of a GaN crystal having reduced dislocation density;

FIG. 8 is a timing chart of the temperature in the crystal growthapparatus shown in FIG. 1;

FIG. 9 is a schematic diagram showing the state inside the reactionvessel and the outer reaction vessel during the interval between twotimings t1 and t2 shown in FIG. 8;

FIG. 10 is a schematic diagram showing the state inside the conduitduring the interval between two timings t4 and t5 shown in FIG. 8;

FIG. 11 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 13 of the present invention;

FIGS. 12A and 12B are schematic diagrams showing another example of thebase body;

FIG. 13 is a schematic diagram showing further example of the base body;

FIGS. 14A-14C are diagrams showing the steps for causing crystal growthof a GaN crystal of reduced threading dislocations on the base bodyshown in FIG. 13;

FIG. 15 is a schematic cross-sectional diagram showing a crystal growthapparatus according to Embodiment 2 of the present invention;

FIGS. 16A and 16B are diagrams showing a support unit shown in FIG. 15in an enlarged scale;

FIG. 17 is a schematic diagram showing the construction of an up/downmechanism shown in FIG. 15;

FIG. 18 is a timing chart showing a vibration detection signal;

FIG. 19 is a schematic diagram showing the state inside the reactionvessel and the outer reaction vessel in the Embodiment 2 during theinterval between two timings t1 and t2 shown in FIG. 8;

FIG. 20 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 2 of the present invention;

FIG. 21 is a schematic diagram showing the state inside the reactionvessel and the outer reaction vessel in the steps S7 and S9 shown inFIG. 20;

FIG. 22 is a schematic diagram showing the state inside the reactionvessel and the outer reaction vessel in the steps S9A shown in FIG. 20;

FIG. 23 is a schematic cross-sectional diagram showing a crystal growthapparatus according to Embodiment 3 of the present invention;

FIG. 24 is a timing chart showing the temperature of the reaction vesseland the outer reaction vessel and a Li concentration in the meltmixture;

FIG. 25 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 3 of the present invention;

FIG. 26 is another schematic cross-sectional diagram showing a crystalgrowth apparatus according to Embodiment 3 of the present invention;

FIG. 27 is another flowchart explaining the manufacturing method of aGaN crystal according to Embodiment 3 of the present invention;

FIG. 28 is another oblique view diagram of the stopper/inlet plugaccording to the present invention;

FIG. 29 is a cross-sectional diagram showing the method for mounting thestopper/inlet plug shown in FIG. 23;

FIGS. 30A and 30B are further oblique view diagrams of the stopper/inletplug according to the present embodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, the present invention will be described for embodimentswith reference to the drawings. In the drawings, those partscorresponding to the parts are designated by the same reference numeralsand the description thereof will be not repeated.

Embodiment 1

FIG. 1 is a schematic cross-sectional diagram showing the constructionof a crystal growth apparatus according to Embodiment 1 of the presentinvention. Referring to FIG. 1, the crystal growth apparatus 100 ofEmbodiment 1 comprises a reaction vessel 10, an outer reaction vessel20, conduits 30 and 40, a stopper/inlet plug 50, heating units 60, 70and 80, gas supply lines 90 and 110, valves 120, 121 and 160, a pressureregulator 130, a gas cylinder 140, an evacuation line 150, a vacuum pump170, a pressure sensor 180, and a metal melt 190.

The reaction vessel 10 has a generally cylindrical form and is formed ofboron nitride (BN). The outer reaction vessel 20 is disposed around thereaction vessel 10 with a predetermined separation from the reactionvessel 10. Further, the outer reaction vessel 20 is formed of a mainpart 21 and a lid 22. Each of the main part 21 and the lid 22 is formedof SUS 316L stainless steel, wherein a metal seal ring is providedbetween the main part 21 and the lid 22 for sealing. Thus, there occursno leakage of a melt mixture 290 to be described later to the outside ofthe reaction vessel 1020.

The conduit 30 has a generally cylindrical pillar-shaped form and isconnected to the outer reaction vessel 20 at the underside of thereaction vessel 10 in terms of a gravitational direction DR1. Theconduit 40 has a generally cylindrical pillar-shaped form and is fixedupon the outer reaction vessel at the upper side of the reaction vessel10 in terms of the gravitational direction DR1 such that a part thereofis inserted into a space 23 inside the outer reaction vessel 20 via theouter reaction vessel 20.

The stopper/inlet plug 50 may be formed of a metal, ceramic, or thelike, for example, and is held inside the conduit 20 at a location lowerthan the connection part of the outer reaction vessel 30 and the conduit30.

The heating unit 60 is disposed so as to surround the outercircumferential surface 20A of the outer reaction vessel 20. On theother hand, the heating unit 70 is disposed so as to face a bottomsurface 20B of the outer reaction vessel 20. The heating unit 80 isdisposed so as to surround a part of the conduit 40.

The gas supply line 90 has an end connected to the outer reaction vessel20 via the valve 120 and the other end connected to the gas cylinder 130via the pressure regulator 140. The gas supply line 110 has an endconnected to the conduit 30 via the valve 121 and the other endconnected to the gas supply line 90.

The valve 120 is connected to the gas supply line 90 in the vicinity ofthe outer reaction vessel 20, the valve 121 is connected to the gassupply line 110 in the vicinity of the conduit 30, the pressureregulator 130 is connected to the gas supply line 90 in the vicinity ofthe gas cylinder 140, and the gas cylinder 140 is connected to the gassupply line 90.

The evacuation line 150 has an end connected to the outer reactionvessel 20 via the valve 160 and the other end connected to the vacuumpump 170. The valve 160 is connected to the evacuation line 150 in thevicinity of the outer reaction vessel 20. The vacuum pump 170 isconnected to the evacuation line 150.

The pressure sensor 180 is mounted to the outer reaction vessel 20. Themetal melt 190 comprises a melt of metal sodium (metal Na) and is heldbetween the reaction vessel 10 and outer the reaction vessel 20 andinside the conduit 30.

The reaction vessel 10 holds the melt mixture 290 containing thereinmetal Na and metal gallium (metal Ga). The outer reaction vessel 20surrounds the reaction vessel 10. The conduit 30 leads the nitrogen gas(N2 gas) supplied from the gas cylinder 140 via the gas supply lines 90and 110 to the stopper/inlet plug 50.

The conduit 40 holds therein the metal Ga 300 and metal lithium (metalLi) 310. The stopper/inlet plug 50 has a dimple structure on the outerperipheral surface such that there are formed apertures of the size ofseveral ten microns between the inner wall of the conduit 30 and thestopper/inlet plug 50. Thus, the stopper/inlet plug 50 allows thenitrogen gas in the conduit 30 to pass in the direction to the metalmelt 190 and supplies the nitrogen gas to the space 23 via the metalmelt 190. Further, the stopper/inlet plug 50 holds the metal melt 190between the reaction vessel 10 and the outer reaction vessel 20 andfurther in the conduit 30 by the surface tension caused by the aperturesof the size of several ten microns.

The heating unit 60 heats the reaction vessel 10 and the outer reactionvessel 20 to the crystal growth temperature from the outer peripheralsurface 20A of the outer reaction vessel 20. The heating unit 70 heatsthe reaction vessel 10 and the outer reaction vessel 20 to the crystalgrowth temperature from the bottom surface 20B of the outer reactionvessel 20. The heating unit 80 heats the metal Ga 300 held in theconduit 40 to 30° C. or higher, wherein it should be noted that themetal Ga has the melting temperature of 30° C.

The gas supply line 90 supplies the nitrogen gas supplied from the gascylinder 140 via the pressure regulator 130 to the interior of the outerreaction vessel 20 via the valve 120. The gas supply line 110 suppliesthe nitrogen gas supplied from the gas cylinder 140 via the pressureregulator 130 to the interior of the conduit 30 via the valve 121.

The valve 120 supplies the nitrogen gas inside the gas supply line 90 tothe interior of the outer reaction vessel 20 or interrupts the supply ofthe nitrogen gas to the interior of the outer reaction vessel 20. Thevalve 121 supplies the nitrogen gas inside the gas supply line 110 tothe conduit 30 or interrupts the supply of the nitrogen gas to theconduit 30. The pressure regulator 130 supplies the nitrogen gas fromthe gas cylinder 140 to the gas supply lines 90 and 110 after settingthe pressure to a predetermined pressure.

The gas cylinder 140 holds the nitrogen gas. The evacuation line 150passes the gas inside the outer reaction vessel 20 to the vacuum pump170. The valve 160 connects the interior of the outer reaction vessel 20and the evacuation line 150 spatially or disconnects the interior of theouter reaction vessel 20 and the evacuation line 150 spatially. Thevacuum pump 170 evacuates the interior of the outer reaction vessel 20via the evacuation line 150 and the valve 160.

The pressure sensor 180 detects the pressure inside the outer reactionvessel 20. The metal melt 190 supplies the nitrogen gas introducedthrough the stopper/inlet plug 50 into the space 23.

FIG. 2 is an oblique view diagram showing the construction of thestopper/inlet plug 50 shown in FIG. 1. Referring to FIG. 2, thestopper/inlet plug 50 includes a plug 51 and projections 52. The plug 51has a generally cylindrical form. Each of the projections 52 has agenerally semi-circular cross-sectional shape and the projections 51 areformed on the outer peripheral surface of the plug 51 so as to extend ina length direction DR2.

FIG. 3 is a plan view diagram showing the state of mounting thestopper/inlet plug 50 to the conduit 30. Referring to FIG. 3, theprojections 52 are formed with plural number in the circumferentialdirection of the plug 51 with an interval d of several ten microns.Further, each projection 52 has a height H of several ten microns. Theplural projections 52 of the stopper/inlet plug 50 make a contact withthe inner wall surface 30A of the conduit 30. With this, thestopper/inlet plug 50 is in engagement with the inner wall of theconduit 30.

Because the projections 52 have a height H of several ten microns andare formed on the outer peripheral surface of the plug 51 with theinterval d of several ten microns, there are formed plural gaps 53between the stopper/inlet plug 50 and the inner wall 30A of the conduit30 with a diameter of several ten microns in the state the stopper/inletplug 50 is in engagement with the inner wall 30A of the conduit 30.

This gap 53 allows the nitrogen gas to pass in the length direction DR2of the plug 51 and holds the metal melt 190 at the same time by thesurface tension of the metal melt 190, and thus, the metal melt 190 isblocked from passing through the gap in the longitudinal direction DR2of the plug 51.

FIG. 4 is a schematic diagram showing the relationship between thenitrogen gas pressure and the crystal growth temperature for the case ofgrowing a GaN crystal. In FIG. 4, the horizontal axis represents thecrystal growth temperature while the vertical axis represents thenitrogen gas pressure. Referring to FIG. 4, a region REG1 represents thereaction where dissolving of the GaN crystal takes place, while a regionREG2 represents the region where there occurs growth of a GaN crystalfrom a seed crystal while suppressing nucleation on the bottom surfaceand sidewall surface of the reaction vessel 10 in contact with the meltmixture 290. Further, a region REG3 represents the region where multiplenucleation takes place.

Thus, with the present invention, growth of the GaN crystal is made inthe region REG2 where there occurs no new nucleation.

FIG. 5 is a diagram showing the relationship between the mole ratio ofmetal Na and metal Ga and the nitrogen gas pressure. In FIG. 5, thevertical axis represents a mole ratio r between the metal Na and themetal Ga, while the horizontal axis represents the nitrogen gaspressure. Here, it should be noted that the mole ratio r between themetal Na and the metal Ga is represented as Na/(Na+Ga). Further, FIG. 5represents the relationship between the mole ratio r and the nitrogengas pressure at the crystal growth temperature of 775° C.

Referring to FIG. 5, it should be noted that the region under the brokenline k1 represents a crystal growth condition in the region REG2 shownin FIG. 4 in which there occurs formation of oblique facets in the GaNcrystal. Further, the region above the broken line k1 represents theregion in which there occurs multiple nucleation. Thus, the crystalgrowth condition that enables formation of the GaN crystal defined bythe oblique facets is given such that the nitrogen gas pressuredecreases relatively when the mole ratio r is increased relatively andthe nitrogen gas pressure increases relatively when the mole ratio r isdecreased relatively. It should be noted that the relationship betweenthe mole ratio r and the nitrogen gas pressure shown in FIG. 5 is notlimited to he crystal growth temperature of 775° C. but is obtained forthe crystal growth temperature in the range of 720-830° C.

Further, it should be noted that a GaN crystal grown in the c axisdirection (<0001>) is obtained when metal Li of predetermined amount isadded in the crystal growth process conducted in the crystal growthcondition under the broken line k1. In this case, the crystal growthcondition that enables formation of a GaN crystal having a flat surfaceis given by Table 1. TABLE 1 Crystal growth temperature 750-825° C.Nitrogen gas pressure 1-5 MPa Ga amount 2.5 g (35.9 mmol) Na amount 0.55g (23.9 mmol) Mol ratio r 0.4 Li amount 2.2-3.2 mg (0.32-0.46 mmol)

It should be noted that the amount of the metal Li shown in Table 1corresponds to the concentration of 0.5-0.8 mol %. Thus, in the case theLi concentration in the melt mixture 290 is in the range of 0.5-0.8 mol%, a GaN crystal having a flat surface and grown in the c-axis directionis obtained.

Further, when the Li concentration in the melt mixture 290 is changedfrom crystal growth condition shown in Table 1 and increased to 1.0 mol% or more from the foregoing range of 0.5-0.8 mol %, there is causedmultiple nucleation, while when the Li concentration in the melt mixture290 is decreased from the foregoing range of 0.5-0.8 mol % to be smallerthan 0.5 mol %, there is obtained a GaN crystal having a dimple surface.

Thus, with this invention, a GaN crystal of flat surface is grown byadding Li to the melt mixture of metal Ga and metal Na with theconcentration of 0.5-0.8 mol %.

FIG. 6 is a schematic diagram showing the construction of the base body5 shown in FIG. 1. Referring to FIG. 6, the base body 5 comprises asapphire substrate 501 and a GaN film 502. The GaN film 502 is formed ona principal surface 501A of the sapphire substrate 501 by a metalorganic chemical vapor deposition (MOCVD) process. The GaN film 502 thusformed has threading dislocations 5021 with dislocation density in therange of 10⁶-10¹⁰ cm⁻².

With this invention, a GaN crystal is grown on the base body 5 under thecrystal growth condition that forms the oblique facets as describedabove (the region under the broken line k1 shown in FIG. 5) so as togrowth the GaN crystal on the GaN film 502 shown in FIG. 6 with adislocation density smaller than the dislocation density of the GaN film502. Thereafter, a GaN crystal having a flat surface is grown under thecrystal growth condition shown in Table 1.

FIGS. 7A-7F are diagrams showing the process steps for causing crystalgrowth of a GaN crystal having reduced dislocation density. Referring tothe step of FIG. 7A, the base body 5 is manufactured by forming the GaN502 on the sapphire substrate 501 by the MOCVD process.

Further, a GaN crystal is grown on the GaN film 502 of the base body 5under the condition of forming the oblique facets (the region under thebroken line k1 shown in FIG. 5). With this, a number of domains 510 ofGaN crystal are formed on the GaN film 502 (see FIG. 7B).

Further, with continuous growth of the GaN crystal is continued underthe condition of forming the oblique facets (the region under the brokenline k1 shown in FIG. 5), there occurs growth in the domains 510 (seeFIG. 7C), while when the crystal growth of the GaN crystal proceedsfurther, the domains 510 merge with each other, and there are formedlarge domains 520 having oblique facets (see FIG. 7D).

With further growth of the domains 520, there is formed a GaN crystal530 in the form of aggregate of the domains 520, wherein the threadingdislocations 5021 formed in the GaN film 502 on the base body 5 invadeinto the domains 510 and further to the domains 520. There, thethreading dislocations 5021 are deflected in the in-plane direction ofthe sapphire substrate 501 by the oblique facets 521 in the domains 520and are accumulated in the region between adjacent domains 520 and 520(see FIG. 7E).

Thereafter, crystal growth of the GaN crystal is conducted under thecrystal growth condition shown in Table 1. With this, a GaN crystal 550having a flat surface is obtained wherein the GaN crystal 550 thusobtained is formed of a domain 540 grown in the c-axis direction. TheGaN crystal 550 has threading dislocations 551 formed between adjacentdomains 540. In the GaN crystal 550, each domain 540 is characterized bylow dislocation density (ideally no dislocations), and thus, the densityof the threading dislocations 551 becomes lower than the density of thethreading dislocations 5021 in the GaN film 502 (see FIG. 7F).

Thus, it becomes possible to manufacture the GaN crystal 550 having adislocation density lower than that of the GaN film 502, by growing theGaN crystal 530 on the base body 5 under the condition where the obliquefacets are formed, and subsequently growing a GaN crystal under thecondition where the GaN crystal has a flat surface.

In this way, the GaN crystal 530 functions to deflect the threadingdislocations of the GaN film 502 forming the base body 5 in the in-planedirection of the sapphire substrate 501. Further, it should be notedthat the density of the threading dislocations 540 in the GaN crystal550 is determined by the size of the domains 520 in the GaN crystal 530.

In more detail, the density of the threading dislocations 540 in the GaNcrystal 550 is decreased relatively when the size of the domain 520 isincreased relatively. Further, the density of the threading dislocationsis increased relatively when the size of the domain 520 is decreasedrelatively.

This means that it is important to increase the size of the domains 520for reducing the density of the threading dislocations 540. Thus, itbecomes possible to manufacture the GaN crystal 550 having a dislocationdensity lower than that of the GaN film 502, by growing the GaN crystal530 on the base body 5 under the condition where the oblique facets areformed, and subsequently growing a GaN crystal under the condition wherethe GaN crystal has a flat surface.

Incidentally, it should be noted that the oblique facets 521 has thesurface orientation of (10-11), for example. It should be noted thatthis surface orientation (10-11) represents the surface orientationrepresented in FIG. 7E.

FIG. 8 is a timing chart of the temperature in the crystal growthapparatus 100 shown in FIG. 1. Further, FIG. 9 is a schematic diagramshowing the state inside the inner 10 and the outer reaction vessel 20during the interval between two timings t1 and t2 shown in FIG. 8.Further, FIG. 10 is a schematic diagram showing the state inside theconduit 40 during the interval between two timings t4 and t5 shown inFIG. 8.

In FIG. 8, it should be noted that the curve k2 represents thetemperature of the reaction vessel 10 and the outer reaction vessel 20while the curve k3 represent the temperature of the conduit 40.

Referring to FIG. 8, the heating units 60 and 70 heat the reactionvessel 10 and the outer reaction vessel 20, such that the temperaturesthereof rise along the line k1 and are held at 800° C. When the heatingunits 60 and 70 start to heat the reaction vessel 10 and the outerreaction vessel 20, the temperature of the reaction vessel 10 and theouter reaction vessel 20 start to rise and reach a temperature of 98° C.at the timing t1 and a temperate of 800° C. at the timing t2.

With this, the metal Na held between the reaction vessel 10 and theouter reaction vessel 20 undergoes melting and the metal melt 190(=metal Na liquid) is formed. Further, the nitrogen gas 4 inside thespace 23 cannot escape to the space 31 inside the conduit 30 through themetal melt 190 (=metal Na melt) and the stopper/inlet plug 50, and thenitrogen gas 4 is confined into the space 23. Reference should be madeto FIG. 9.

Further, when the temperatures of the reaction vessel 10 and the outerreaction vessel 20 have reached 800° C., there occurs melting of themetal Na and metal Ga in the reaction vessel 10 and the melt mixture 290is formed in the reaction vessel 10. Thereby, the nitrogen gas 4 in thespace 23 is incorporated into the melt mixture 290 via the meditatingmetal Na in the melt mixture 290, and there occurs growth of the GaNcrystal 530 on the GaN film 502 of the base body 5. Thereafter, thecrystal growth of the GaN crystal 530 is continued during the intervalfrom the timing t2 to the timing t3, wherein the heating unit 80 heatsthe part of the conduit 40 that holds the metal Ga 300 to thetemperature Ts1.

Here, the temperature Ts1 is set to be higher than the meltingtemperature of metal Ga (30° C.) but lower than the melting temperatureof metal Na (98° C.).

When the part of the conduit 40 holding the metal Ga 300 is heated to30° C. or higher, the metal Ga 300 undergoes melting and a Ga melt 301is formed as a result. The Ga melt 301 then enters to the melt mixture290 along the inner wall of the conduit 40, and the metal Li 310 entersthe melt mixture 290 by falling through the conduit 40 by gravity (seeFIG. 10).

The metal Li thus entered into the melt mixture 290 undergoes dissolvinginto the melt mixture 290 held at 800° C. in view of the meltingtemperature of 180° C. for metal Li, and there occurs crystal growth ofthe GaN crystal 550 from the timing t5 to the timing t6.

Thus, the metal Li 310 is held in the conduit 40 with the weight of2.2-3.2 mg as represented in Table 1. With this, the GaN crystal 550 isformed during the interval from the timing t5 to the timing t6 with flatsurface, wherein the GaN crystal 550 thus formed is grown in the c-axisdirection.

Further, because the GaN crystal 530 is grown during the interval fromthe timing t2 to the timing t3, Ga in the melt mixture 290 is decreasedand the mole ratio r between Ga and Na increases beyond 0.4 withprogress of time from the timing t2 to the timing t3. Thus, the weightof the metal Ga 300 that holds the metal Li 310 in the conduit 40 is setsuch that the mole ratio r of the melt mixture 290 becomes about 0.4 inthe event the Ga melt 310 has entered into the melt mixture 290 afterthe timing t4.

FIG. 11 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 1 of the present invention. Referring toFIG. 11, the reaction vessel 10 and the outer reaction vessel 20 areincorporated into a glove box filled with an Ar gas when a series ofprocesses are started. Further, the base body 5 is loaded into thereaction vessel 10 in an Ar gas ambient (step S1), and the metal Na andmetal Ga are loaded to the reaction vessel 10 in the Ar gas ambient(step S2). In this case, the metal Na and the metal Ga are loaded intothe reaction vessel 10 such that the mole ratio r becomes 0.4. The Argas should be the one having a water content of 10 ppm or less and anoxygen content of 10 ppm or less (this applied throughout the presentinvention).

Thereafter, the metal Na is loaded between the reaction vessel 10 andthe outer reaction vessel 20 in an Ar gas ambient (step S3), and themetal Li 310 of 2.2-3.2 mg is loaded into the conduit 40 in an Ar gasambient. Thereafter, the metal Li 310 thus loaded is covered by themetal Ga 300 (step S4).

Next, the reaction vessel 10 and the outer reaction vessel 20 are set inthe crystal growth apparatus 100 in the state that the reaction vessel10 and the outer reaction vessel 20 are filled with the Ar gas.

Next, the valve 160 is opened and the Ar gas filled in the reactionvessel 10 and the outer reaction vessel 20 is evacuated by the vacuumpump 170. In this case, the Ar gas in the space of the conduit 40 inwhich the metal Li is held is evacuated through the gap between themetal Ga 300 and the conduit 40.

After evacuating the interior of the reaction vessel 10 and the outerreaction vessel 20 to a predetermined pressure (0.133 Pa or lower) bythe vacuum pump 170, the valve 160 is closed and the valves 120 and 121are opened. Thereby, the reaction vessel 10 and the outer reactionvessel 20 are filled with the nitrogen gas from the gas cylinder 140 viathe gas supply lines 90 and 110. In this case, the nitrogen gas issupplied to the reaction vessel 10 and the outer reaction vessel 20 viathe pressure regulator 130 such that the pressure inside the reactionvessel 10 and the outer reaction vessel 20 becomes about 0.1 MPa.

Further, when the pressure inside the outer reaction vessel 20 asdetected by the pressure sensor 180 has reached about 0.1 MPa, thevalves 120 and 121 are closed and the valve 160 is opened. With this thenitrogen gas filled in the reaction vessel 10 and the outer reactionvessel 20 is evacuated by the vacuum pump 170. In this case, too, theinterior of the reaction vessel 10 and the outer reaction vessel 20 isevacuated to a predetermined pressure (0.133 Pa or less) by using thevacuum pump 170.

Further, this vacuum evacuation of the reaction vessel 10 and the outerreaction vessel 20 and filling of the nitrogen to the reaction vessel 10and the outer reaction vessel 20 are repeated several times.

Thereafter, the interior of the reaction vessel 10 and the outerreaction vessel 20 is evacuated to a predetermined pressure by thevacuum pump 170, and the valve 160 is closed. Further, the valves 120and 121 are opened and the nitrogen gas is filled into the reactionvessel 10 and the outer reaction vessel 20 by the pressure regulator 130such that the pressure of the reaction vessel 10 and the outer reactionvessel 20 becomes the range of 1.01-5.05 MPa (step 5).

Because the metal Na held between the reaction vessel 10 and the outerreaction vessel 20 is solid in this state, the nitrogen gas is suppliedto the space 23 inside the outer reaction vessel 20 also from the space31 of the conduit 30 via the stopper/inlet plug 50. When the pressure ofthe space 23 as detected by the pressure sensor 180 has become 1.01-5.05Pa, the valve 120 is closed.

Thereafter, the reaction vessel 10 and the outer reaction vessel 20 areheated to 800° C. by the heating units 60 and 70 (step S6). In thisprocess of heating the reaction vessel 10 and the outer reaction vessel20 to 800° C., the metal melt Na held between the reaction 10 and theouter reaction vessel 20 undergoes melting in view of the meltingtemperature of metal Na of about 98° C., and the metal melt 190 isformed. Thereby, two vapor-liquid interfaces 1001 and 1002 are formed.Reference should be made to FIG. 1. The vapor-liquid interface 1 islocated at the interface between the metal melt 190 and the space 23 inthe outer reaction vessel 20, while the vapor-liquid interface 2 islocated at the interface between the metal melt 190 and thestopper/inlet plug 50.

At the moment the temperatures of the reaction vessel 10 and the outerreaction vessel 20 are elevated to 800° C., the temperature of thestopper/inlet plug 50 becomes 150° C. This means that the vapor pressureof the metal melt 190 (=metal Na melt) at the vapor-liquid interface 2is 7.6×10⁻⁴ Pa, and thus, there is caused little evaporation of themetal melt 190 (=metal Na melt) through the gaps 53 of the stopper/inletplug 50. As a result, there occurs little decrease of the metal melt 190(=metal Na melt).

Further, even when the temperature of the stopper/inlet plug 50 iselevated to 300° C. or 400° C., the vapor pressure of the metal melt 190(=metal Na melt) is only 1.8 Pa and 47.5 Pa, respectively, and decreaseof the metal melt 190 (=metal Na melt) by evaporation is almostignorable with such a vapor pressure.

Thus, with the crystal growth apparatus 100, the temperature of thestopper/inlet member 50 is set to a temperature such that there occurslittle decrease of the metal melt 190 (=metal Na melt) by way ofevaporation.

Further, during the step in which the inner reaction vessel 10 and theouter reaction vessel 20 are heated to 800° C., the metal Na and themetal Ga inside the reaction vessel 10 become a liquid, and the meltmixture 290 of metal Na and metal Ga is formed in the reaction vessel10.

Further, when the temperatures of the reaction vessel 10 and the outerreaction vessel 20 are elevated to 800° C., the nitrogen gas in thespace 23 is incorporated into the melt mixture 290 via the mediatingmetal Na, and there starts the growth of GaN crystal 530 on the GaN film502 of the base body 5 under the condition in which the oblique facetsare formed.

Thereafter, the temperatures of the reaction vessel 10 and the outerreaction vessel 20 are held at 800° C. during a predetermined interval(from timing t2 to timing t3), and there proceeds crystal growth of theGaN crystal 530 under the condition where the oblique facets are formed.Thus, with progress of crystal growth of the GaN crystal 530, thenitrogen gas in the space 23 is consumed and there is caused a decreaseof the nitrogen gas in the space 23. Then the pressure P1 of the space23 becomes lower than the pressure P2 of the space 30 inside the conduit31 (P1<P2), and there is formed a differential pressure between thespace 23 and the space 31. Thus, the nitrogen gas in the space 31 issupplied to the space 23 consecutively via the stopper/inlet plug 50 andthe metal melt 190 (=metal Na melt).

Thus, the temperatures of the reaction vessel 10 and the outer reactionvessel 20 are held at 800° C. for a predetermined duration whilesupplying the nitrogen gas to the reaction vessel 10 and the space 23 ofthe outer reaction vessel 20. With this, the GaN crystal 530 is grownunder the condition in which there are formed oblique facets.

At the timing t3, the heating unit 80 heats the part of the conduit 40holding the metal Ga 300 to the temperature Ts1, and the Ga melt 301 andthe metal Li 310 are loaded into the melt mixture 290 (step S8).

Thereafter, the temperatures of the reaction vessel 10 and the outerreaction vessel 20 are held at 800° C. for a predetermined duration(from timing t5 to timing t6) while supplying the nitrogen gas to thereaction vessel 10 and the space 23 of the outer reaction vessel 20(step S9). With this, growth of the GaN crystal 550 takes place withflat surface.

Thereafter, the temperatures of the reaction vessel 10, the outerreaction vessel 20 and the conduit 40 are lowered (step S10), andmanufacture of the GaN crystal is completed.

As explained heretofore, the manufacturing method of the GaN crystal ofthe present invention has the feature of growing the GaN crystal 530 onthe base body 5 under the condition that there are formed oblique facetson the GaN crystal 530 (reference should be made to the step S7).Thereafter, the GaN crystal 550 is grown on the base body 5 under thecondition that a flat surface is obtained (see the step S9).

As a result of this feature, the threading dislocations originating fromthe threading dislocations 5021 in the GaN film 502 formed on the basebody 5 are deflected in the in-plane direction of the sapphire substrate501 by the oblique facets 521 of the GaN crystal 530, and it becomespossible to manufacture the GaN crystal 550 with reduced threadingdislocation density. In the present case, it is possible to reduce thedensity of the threading dislocations in the GaN crystal 550 to about10⁴ cm⁻².

Further, it should be noted that the GaN crystals 530 and 550 grownaccording to the flowchart shown in FIG. 11 contain Na, and the GaNcrystal contains Li with the concentration of 10¹⁵-10²¹ cm⁻³.

Further, the manufacturing method of GaN crystal of the presentinvention has the feature of growing the GaN crystal in the state inwhich the metal Na vapor 7 is confined in the space 23 (see FIG. 9). Asa result of this feature, evaporation of metal Na from the melt mixture290 is suppressed, and it becomes possible to maintain the crystalgrowth rate of the GaN crystal by incorporating the nitrogen gas 4 inthe space 23 into the melt mixture 290.

In the steps S7 and S9 shown in FIG. 11, it should be noted that thetemperatures of the reaction vessel 10 and the outer reaction vessel 20are held at 800° C. in the interval from the timing t2 to the timing t6,and the growth of the GaN crystal 530 is in progress on the base body 5.Further, with progress of growth of the GaN crystal 530, there occursevaporation of metal Na from the metal melt 190 and the melt mixture290, and thus, there exist a mixture of the nitrogen gas 4 and the metalNa vapor 7 in the space 23 (see FIG. 9).

Further, with consumption of the nitrogen gas 4, the pressure P1 of thespace 23 is lowered than the pressure P2 of the space 31 inside theconduit 30. Then the nitrogen gas is supplied from the space 31 of theconduit 30 to the metal melt 190 via the stopper/inlet plug 50, whereinthe nitrogen gas is moved through the metal melt 190 in the form ofbubbles 191. Thus, the nitrogen gas is supplied to the space 23 throughthe vapor-liquid interface 1 (see FIG. 9).

Now, when the pressure P1 of the space 23 becomes generally equal to thepressure P2 inside the space 31, the supply of the nitrogen gas from thespace 30 of the conduit 31 to the reaction vessel 50 and the outerreaction vessel 10 via the stopper/inlet plug 20 and the metal melt 190is stopped.

Thus, the stopper/inlet plug 50 holds the metal melt 190 (=metal Namelt) between the reaction vessel 10 and the outer reaction vessel 20and also inside the conduit 30 by the surface tension of the metal melt190 and further supplies the nitrogen gas from the space 31 to thereaction vessel 10 and the outer reaction vessel 20. Thus, thestopper/inlet plug 50 is formed of a structure that blocks passage ofthe metal melt 190 therethrough.

While it has been explained in the foregoing that the manufacturing ofthe GaN crystal 530 of reduced threading dislocations is made on thebase body 5, which in turn comprises the sapphire substrate 501 and theGaN film 502 formed on the sapphire substrate 501 by an MOCVD process,the present invention is not limited to such a specific example and itis also possible to use a seed crystal of a GaN crystal for the basebody 5.

FIGS. 12A and 12B are schematic diagrams showing other examples of thebase body 5. Thus, the base body 5 may be formed of a base body 5A shownin FIG. 12A or a base body 5B shown in FIG. 12B.

Referring to FIG. 12A, the base body 5A comprises a seed crystal 560 ofa columnar shape. The seed crystal 560 contains threading dislocations561.

In the region REG3 shown in FIG. 4, there are caused numerous nucleationon the sidewall surface and bottom surface of the reaction vessel 10that make contact with the melt mixture 290. Further, the nuclei thusformed have a columnar shape grown in the c-axis direction. Thus, alarge number of GaN crystals are grown with the crystal growth apparatus100 under the crystal growth condition corresponding to the recon R% EG3shown in FIG. 4. Thus, one GaN is picked up from the numerous GaNcrystals thus grown and is used for the seed crystal 560.

In the case of growing a GaN in the region REG3 shown in FIG. 4, itshould be noted that the mole ratio r between the metal Na and the metalGa is set to 5:5, for example.

Referring to FIG. 12B, the base body 5B comprises a seed crystal 570 andGaN crystal s 580 and 590. The seed crystal 570 is manufactured underthe crystal growth condition corresponding to the region REG3 shown inFIG. 4 and is formed of a dislocation-free GaN crystal. It should benoted that the GaN crystal 580 is grown from the seed crystal 570 underthe crystal growth condition corresponding to the region REG2 shown inFIG. 4 and is dislocation-free. The GaN crystal 590 is grown incontinuation to the GaN crystal 580 under the crystal growth conditioncorresponding to the region REG2 shown in FIG. 4 and containsdislocations 591.

Thus, the base body 5B is manufactured by growing a GaN crystal from theseed crystal 570 under the crystal growth condition of the region REG2shown in FIG. 4. Thereby, there occurs crystal growth ofdislocation-free GaN crystal 580 at first, and growth of the GaN crystalcontaining therein dislocations 590 takes place subsequently.

Thus, FIG. 12A shows the case in which the seed crystal 560 grown underthe crystal growth condition corresponding to the region REG3 shown inFIG. 4 contains itself the threading dislocations 561, while FIG. 12Bshows the case in which the GaN crystal grown from the seed crystal 570manufactured by using the crystal growth condition corresponding to theregion REG3 shown in FIG. 4 contains the dislocations 591.

In any of the cases of using the base body 5A or base body 5B, the GaNcrystal 550 grown according to the flowchart shown in FIG. 11 hasreduced threading dislocations. In this case, the base body 5A or 5B isdisposed at the bottom surface of the reaction vessel 10 in the step S1.

Thus, in any of the cases of using the base body 5A or 5B of GaNcrystal, it is possible to manufacture the GaN crystal 550 with reducedthreading dislocations.

FIG. 13 is a schematic diagram showing another example of base body 5.Thus, the base body 5 may be formed of a base body 5C shown in FIG. 13.Referring to FIG. 13, the base body 5C comprises the sapphire substrate501 and plural GaN films 503. The plural GaN films 503 are manufacturedby etching the GaN film 502 formed according to an MOCVD process (seeFIG. 6) with a predetermined width W and a predetermined interval L.Thus, each GaN film 503 comprises a stripe-form crystal having the widthW. Further, each of the plural GaN crystals 503 has threadingdislocations 5031. The predetermined width W may be set to 100 μm, forexample, while the predetermined interval L may be set to 300 μm, forexample.

FIGS. 14A-14C are diagrams showing the steps for causing crystal growthof a GaN crystal of reduced threading dislocations on the base bodyshown in FIG. 13. Referring to FIGS. 14A, a GaN crystal is grown on theGaN film 502 of the base body 5C under the condition of forming theoblique facets (the region under the broken line k1 shown in FIG. 5).With this, a number of domains 600 of GaN crystal are formed on theplural GaN films 503 of the base body 5C (see FIG. 14A).

Further, with continuous growth of the GaN crystal is continued underthe condition of forming the oblique facets (the region under the brokenline k1 shown in FIG. 5), there occurs growth in the domains 600 (seeFIG. 7C), while when the crystal growth of the GaN crystal proceedsfurther, the domains 600 merge with each other, and there are formedlarge domains 610 having oblique facets 611 (see FIG. 14B).

With further growth of the domains 610, there is formed a GaN crystal630 in the form of aggregate of the domains 620, wherein the threadingdislocations 5031 formed in the GaN film 503 on the base body 5C invadeinto the domains 600 and further to the domains 610. There, thethreading dislocations 5031 are deflected in the in-plane direction ofthe sapphire substrate 501 by the oblique facets 611 in the domains 610and are accumulated in the region between adjacent domains 620 and 620(see FIG. 14C).

Thereafter, crystal growth of the GaN crystal is conducted under thecrystal growth condition shown in Table 1. With this, a GaN crystal offlat surface is obtained from the domains grown in the c-axis directionsimilarly to the GaN crystal 550 shown in FIG. 7E.

As a result, it becomes possible to manufacture a GaN crystal withreduced threading dislocations.

In the case of using the base body 5C, the domains 600 are not formed onthe part of the base body 5C where the sapphire substrate 501 isexposed, and thus, it becomes possible to increase the size of thedomains 620 as compared with the case of using the base body 5.

Thus, it is possible with the present embodiment to decrease thethreading dislocations in the GaN crystal grown on the domains 620 ascompared with the case of using the base body 5. Further, it becomespossible to increase the size of the GaN crystal grown on the domains620 further as compared with the case of using the base body 5, and itbecomes possible to manufacture a device by using a dislocation-free GaNcrystal.

In the case of using the base body 5C, the interval L of the GaN films503 having the threading dislocations 5031 is determined according to hesize of the semiconductor device that is manufactured by using the GaNcrystal 550 of flat surface. In the case of manufacturing asemiconductor device by using the GaN crystal 550, the semiconductordevice is formed in the domain 540 where there is no threadingdislocation. Further, the size of the domains 540 free from threadingdislocations is determined in the GaN crystal 550 grown on the GaNcrystal 630, which in turn is formed of aggregate of the domains 620,according to the interval L. Thus, the interval L is determinedaccording to the size of the semiconductor device to be manufactured byusing the GaN crystal 550.

With the present embodiment, it is also possible to use the sapphiresubstrate 501 for the base body by removing the GaN crystal 502 from thebase body 5.

Further, with the present invention, it is possible to manufacture thebase body 5 by using ScAlMgO in place of the sapphire substrate 501 ofthe base body 5.

Further, it is possible to use a SiC crystal for the base body in placeof the base body 5.

In the case of growing the GaN crystal of reduced threading dislocationsby using the crystal growth apparatus 100, it is also possible to growthe GaN crystal of reduced threading dislocations as follows.

Thus, with the crystal growth apparatus 100, the temperature T1, whichis the temperature of the vapor-liquid interface 1 between the space 23inside the outer reaction vessel 20 and the metal liquid 190 or thetemperature near the vapor-liquid interface 1, and the temperature T 2,which is the temperature of the vapor-liquid interface 3 between thespace 23 and the melt mixture 290 or the temperature near thevapor-liquid interface 3, are set to the respective temperatures suchthat the vapor pressure of the metal Na evaporated from the metal melt190 is generally identical with the vapor pressure of the metal Naevaporated from the melt mixture 290.

When these two temperatures are identical, the vapor pressure of themetal Na evaporated from the metal melt 190 becomes higher than thevapor pressure of the metal Na evaporated from the melt mixture 290, andthus, the temperature T1 is set to be lower than the temperature T2 suchthat the vapor pressure of the metal Na evaporated from the metal melt190 becomes generally identical with the vapor pressure of the metal Naevaporated from the melt mixture 290.

As a result, migration of the metal Na from the metal melt 190 to themelt mixture 290 balances with migration of the metal Na from the meltmixture 290 to the metal melt 190, and it becomes possible to suppressthe change of molar ratio of the metal Na and the metal Ga in the meltmixture 290 caused by the migration of the metal Na from the metal melt190 to the melt mixture 290 or from the melt mixture 290 to the metalmelt 190. Thereby, it becomes possible to manufacture a GaN crystal oflarge size stably.

Further, while it has been explained that the height H of theprojections 52 of the stopper/inlet plug 50 and the separation d betweenthe projections 52 are explained as several ten microns, it is possiblethat the height H of the projections 52 and the separation d between theprojections 52 may be determined by the temperature of the stopper/inletplug 50. More specifically, when the temperature of the stopper/inletplug 50 is relatively high, the height H of the projections 52 is setrelatively higher and the separation d between the projections 52 is setrelatively smaller. Further, when the temperature of the stopper/inletplug 50 is relatively low, the height H of the projection 52 is setrelatively lower and the separation d between the projections 52 is setrelatively larger. Thus, in the case the temperature of thestopper/inlet plug 50 is relatively high, the size of the gap 53 betweenthe stopper/inlet plug 50 and the conduit 30 is set relatively small,while in the case the temperature of the stopper/inlet plug 50 isrelatively high, the size of the gap 53 between the stopper/inlet plug50 and the conduit 30 is set relatively larger.

It should be noted that the size of the cap 52 is determined by theheight H of the projections 52 and the separation d between the pluralprojections 52, while the size of the gap 53 capable of holding themetal melt 190 by the surface tension changes depending on thetemperature of the stopper/inlet plug 50. Thus, the height H of theprojections 52 and the separation d between the projections 52 arechanged depending on the temperature of the stopper/inlet plug 50. Withthis, the metal melt 190 is held reliably by the surface tension.

The temperature control of the stopper/inlet valve 50 is achieved by theheating unit 70. Thus, when the stopper/inlet plug 50 is to be heated toa temperature higher than 150° C., the stopper/inlet plug 50 is heatedby the heating unit 70.

While it has bee explained in the foregoing that the GaN crystal 530deflects the threading dislocations 5021 of the GaN film 502 in thein-plane direction of the sapphire substrate 501, the present inventionis not limited to such a specific construction and any construction maybe used in general as long as it is capable of deflecting the threadingdislocations 5021 of the GaN film 502 in the direction different fromthe direction of crystal growth from the base body 5.

Further, while explanation has been made that the GaN crystal 530 has a(10-11) surface, the present invention is not limited to such a specificcase, and the GaN crystal 530 may generally have a crystal growthsurface other than the surface parallel to the c surface and the surfaceparallel to the c-axis.

Further, while explanation has been made that the GaN crystal 550 isformed of a GaN crystal grown in the c-axis direction, the presentinvention is not limited to such a specific construction, and it isgenerally sufficient that the GaN crystal 550 has a crystal growthsurface generally perpendicular to the direction of crystal growth ofthe GaN crystal 530.

Further, it is sufficient that at least a part of the GaN crystal 530makes contact with the base body 5, 5A, 5B, or 5C. When at least a partof the GaN crystal 530 is in contact with the base body 5, 5A, 5B, or5C, it becomes possible to deflect the direction of the threadingdislocations from the base body 5, 5A, 5B and 5C.

Further, while explanation has been made that the base body 5C containsthe plural GaN crystals 503 of stripe shape formed on the sapphiresubstrate 501, the base body 5C of the present invention may containplural GaN crystal islands formed on the sapphire substrate 501. In thiscase, the plural GaN crystal islands are formed on the sapphiresubstrate 501 with a predetermined interval determined according to thesize of the device manufactured by using the GaN crystal 550.

Further, while explanation has been made that the conduit 40 holds themetal Li 310, the present invention is not limited to such aconstruction and it is also possible that the conduit 40 holds line inplace of the metal Li 310.

Further, the GaN crystal 530 grown under the condition of forming theoblique facets constitute a “first group III nitride crystal”, while theGaN crystal 550 having a flat surface constitutes a “second group IIInitride crystal”.

Further, the GaN crystal 630 grown under the condition where the obliquefacets are formed constitutes the “first group III nitride crystal”.

Further, the GaN films 502 and 503 constitute the “third group IIInitride crystal”.

Further, the plural GaN films 503 constitute “plural stripe crystals”.

Further, the seed crystal 560 or the GaN crystal 590 constitutes a“low-grade seed crystal”.

Embodiment 2

FIG. 15 is a schematic cross-sectional diagram showing a crystal growthapparatus according to Embodiment 2 of the present invention. Referringto FIG. 15, a crystal growth apparatus 100A has a construction generallyidentical with the construction of the crystal growth apparatus 100,except that a bellows 200, support unit 210, an up/down mechanism 220, avibration application unit 230, and a vibration detection unit 240 areadded to the crystal growth apparatus 100 shown in FIG. 1.

The bellows 200 is connected to the outer reaction vessel 20 at alocation above the reaction vessel 10 in terms of the gravitationaldirection DR1. The support unit 210 comprises a cylindrical member and apart thereof is inserted into the space 23 inside the outer reactionvessel 20 via the bellows 200. The up/down mechanism 220 is mounted uponthe support unit 210 at the location above the bellows 200.

The bellows 200 holds the support unit 210 and disconnects the interiorof the outer reaction vessel 20 from outside. Further, the bellows 200is capable of expanding and contracting in the gravitational directionDR1 with movement of the support unit 210 in the gravitational directionDR1. The support unit 210 supports a base body 5A of a GaN crystal at afirst end thereof inserted into outer the reaction vessel 2.

The up/down mechanism 220 causes the support unit 210 to move up anddown in response to a vibration detection signal BDS from the vibrationdetection unit 240 according to a method to be explained later, suchthat the base body 5A makes a contact with a vapor-liquid interface 3between the space 23 and the melt mixture 290.

The vibration application unit 230 comprises a piezoelectric element,for example, and applies a vibration of predetermined frequency to thesupport unit 210. The vibration detection unit 240 comprises anacceleration pickup, for example, and detects the vibration of thesupport unit 210 and outputs the vibration detection signal BDSindicative of the vibration of the support unit 210 to the up/downmechanism 220.

FIGS. 16 is an enlarged diagram showing the construction of the supportunit shown in FIG. 15. Referring to FIG. 16, the support unit 210includes a cylindrical member 211 and fixing members 212 and 213. Thecylindrical member 211 has a generally circular cross-sectional form.The fixing member 212 has a generally L-shaped cross-sectional form andis fixed upon an outer peripheral surface 211A and a bottom surface 211Bof the cylindrical member 211 at the side of a first end 2111 of thecylindrical member 211. Further, the fixing member 213 has a generallyL-shaped cross-sectional form and is fixed upon the outer peripheralsurface 211A and the bottom surface 211B of the cylindrical member 211at the side of a first end 2111 of the cylindrical member 211 insymmetry with the fixing member 212. As a result, there is formed aspace part 214 in the region surrounded by the cylindrical member 211and the fixing members 212 and 213 (see FIG. 16A).

The base body 5A comprises a seed crystal 560 containing thereinthreading dislocations 561, while the seed crystal 560 has a shapefitting the space 214. Further, the base body 5A is supported by thesupport unit 210 by being engaged with the space 214. In the presentcase, the base body 5A makes a contact with the bottom surface 211B ofthe cylindrical member 211. Reference should be made to FIG. 16B.

FIG. 17 is a schematic diagram showing the construction of the up/downmechanism 220 shown in FIG. 15. Referring to FIG. 17, the up/downmechanism 220 comprises a toothed member 221, a gear 222, a shaft member223, a motor 224 and a control unit 225.

The toothed member 221 has a generally triangular cross-sectional shapeand is fixed upon the outer peripheral surface 211A of the cylindricalmember 211. The gear 222 is fixed upon an end of the shaft member 223and meshes with the toothed member 221. The shaft member 223 has theforegoing end connected to the gear 222 and the other end connected to ashaft (not shown) of the motor 224.

The motor 224 causes the gear 222 to rotate in the direction of an arrow226 or an arrow 227 in response to control from the control unit 225.The control unit 225 controls the motor 224 based on the vibrationdetection signal BDS from the vibration detection unit 240 and causesthe gear 222 to rotate in the direction of the arrow 226 or 227.

When the gear 222 is rotated in the direction of the arrow 226, thesupport unit 210 moves in the upward direction in terms of thegravitational direction DR1, while when the gear 222 is rotated in thedirection of the arrow 227, the support unit 210 is moved downward interms of the gravitational direction DR1.

Thus, rotation of the gear 222 in the direction of the arrow 226 or 227corresponds to a movement of the support unit 210 up or down in terms ofthe gravitational direction DR1.

FIG. 18 is a timing chart of the vibration detection signal BDS.Referring to FIG. 18, the vibration detection signal BDS detected by thevibration detection unit 240 comprises a signal component SS1 in thecase the base body 5A is not in contact with the melt mixture 290, whilein the case the base body 5A is in contact with the melt mixture 290,the vibration detection signal BDS is formed of a signal component SS2.Further, in the case the base body 5A is dipped into the melt mixture290, the vibration detection signal BDS is formed of a signal componentSS3.

In the event the seed base body 5A is not in contact with the meltmixture 290, the base body 5A is vibrated vigorously by the vibrationapplied by the vibration application unit 230 and the vibrationdetection signal BDS is formed of the signal component SS1 of relativelylarge amplitude. When the base body 5A is in contact with the meltmixture 290, the base body 5A cannot vibrate vigorously even when thevibration is applied from the vibration application unit 230 because ofthe viscosity of the melt mixture 290, and thus, the vibration detectionsignal BDS is formed of the signal component SS2 of relatively smallamplitude. Further, when the base body 5A is dipped into the meltmixture 290, vibration of the base body 5A becomes more difficultbecause of the viscosity of the melt mixture 290, and the vibrationdetection signal BDS is formed of the signal component SS3 of furthersmaller amplitude than the signal component SS2.

Referring to FIG. 17, again, the control unit 225 detects, uponreception of the vibration detection signal from the vibration detectionunit 240, the signal component in the vibration detection signal BDS.Thus, when the detected signal component is the signal component SS1,the control unit 225 controls the motor 224 such that the support unit210 is lowered in the gravitational direction DR1, until the signalcomponent SS2 is detected for the signal component of the vibrationdetection signal BDS .

More specifically, the control unit 225 controls the motor 224 such thatthe gear 222 is rotated in the direction of the arrow 227, and the motor224 causes the gear 222 to rotate in the direction of the arrow 227 inresponse to the control from the control unit 225 via the shaft member223. With this, the support member 210 moves in the downward directionin terms of the gravitational direction.

Further, the control unit 225 controls the motor 224 such that therotation of the gear 222 is stopped when the signal component of thevibration detection signal BDS received from the vibration detectionunit 240 has changed from the signal component SS1 to the signalcomponent SS2, and the motor stops the rotation of the gear 222 inresponse to the control from the control unit 225. With this, thesupport unit 210 stops the movement thereof and the base body 5A is heldat the vapor-liquid interface 3.

On the other hand, the control unit 225 controls the motor 224, whenreceived the vibration detection signal BDS formed of the signalcomponent SS2 from the vibration detection unit 240, such that themovement of the support unit 210 is stopped. In this case, the base body5A is already in contact with the melt mixture 290.

Thus, the up/down mechanism 220 moves the support unit 50 in thegravitational direction DR1 based on the vibration detection signal BDSdetected by the vibration detection unit 240, such that the base body 5Ais in contact with the melt mixture 290.

FIG. 19 is a schematic diagram showing the state inside the reactionvessel 10 and the outer reaction vessel 20 in the Embodiment 2 duringthe interval between two timings t1 and t2 shown in FIG. 8. When theheating units 60 and 70 start to heat the reaction vessel 10 and theouter reaction vessel 20, the temperature of the reaction vessel 10 andthe outer reaction vessel 20 start to rise and reach a temperature of98° C. at the timing t1 and a temperate of 800° C. at the timing t2.

With this, the metal Na held between the reaction vessel 10 and theouter reaction vessel 20 undergoes melting and the metal melt 190(=metal Na liquid) is formed. Further, the nitrogen gas 4 inside thespace 23 cannot escape to the space 31 inside the conduit 30 through themetal melt 190 (=metal Na melt) and the stopper/inlet plug 50, and thenitrogen gas 4 is confined into the space 23. Reference should be madeto FIG. 19.

Further, during the interval from the timing t1 in which the temperatureof the reaction vessel 10 and the outer reaction vessel 20 reaches 98°C. to the timing t2 in which the temperature of the reaction vessel 10and the outer reaction vessel 20 reaches 800° C., it should be notedthat the up/down mechanism 220 moves the support unit 210 up and downaccording to the method explained above in response to the vibrationdetection signal BDS from the vibration detection unit 240 and maintainsthe base body 5A in contact with the melt mixture 290.

When the temperatures of the reaction vessel 10 and the outer reactionvessel 20 have reached 800° C., the nitrogen gas 4 in the space 23 isincorporated into the melt mixture 290 via the mediating metal Naexisting in the melt mixture 290. In this case, it should be noted thatthe concentration of nitrogen in the melt mixture 290 takes the maximumvalue in the vicinity of the vapor-liquid interface 3 between the space23 and the melt mixture 290, and thus, growth of the GaN crystal startsfrom the base body 5A in contact with the vapor-liquid interface 3.

Thereafter, the GaN crystal is grown from the base body 5A during theinterval from the timing t2 to the timing t3 under the condition wherethe oblique facets are formed (the region under the broken like k1 shownin FIG. 5) as explained with reference to FIG. 8, and the GaN crystal offlat top surface is grown thereafter during the interval from the timingt5 to the timing t6.

FIG. 20 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 2 of the present invention. It should benoted that the flowchart of FIG. 20 is identical to the flowchart shownin FIG. 11 except that the step S1 of the flowchart shown in FIG. 11 isreplaced with a step S1A and steps S6A and S9A are added.

Referring to FIG. 20, the reaction vessel 10 and the outer reactionvessel 20 are incorporated into a glove box filled with an Ar gas when aseries of processes are started. Further, the base body 5A is placedabove the reaction vessel 10 in the Ar gas ambient (step S1A). Morespecifically, the base body 5A is set above the reaction vessel 10 byfitting the base body 5A to the space 214 formed on an end 2111 of thesupport unit 210.

Thereafter the steps S2-S6 are executed, and during the process in whichthe inner reaction vessel 10 and the outer reaction vessel 20 are heatedto 800° C., the metal Na and the metal Ga inside the reaction vessel 10become a liquid. Thus, the melt mixture 290 of metal Na and metal Ga isformed in the reaction vessel 10. Next, the up/down mechanism 220 causesthe base body 5A to make a contact with the melt mixture 290 (step S6A).

Thereafter, the foregoing steps S7-S9 are executed. Further, in thesteps S7 and S9, the up/down mechanism 220 lowers the base body 5A whilethe crystal growth of the GaN crystal is in progress as explainedpreviously, such that the base body 5A makes a contact with the meltmixture 290. Thereafter, the foregoing step S10 is carried out andmanufacturing of the GaN crystal of reduced threading dislocations iscompleted.

Thus, it becomes possible to reduce the threading dislocations in theGaN crystal 550 also in the case of causing the base body 5A to make acontact with the surface of the melt mixture 290 (=interface 3) suchthat there occurs growth of the GaN crystal 530 with oblique facets andsuch that there occurs further growth of the GaN crystal 550 of flatsurface.

In the flowchart shown FIG. 20, explanation was made such that the basebody 5A is contacted with the melt mixture 190 of the metal Na and themetal Ga when the reaction vessel 10 and the outer reaction vessel 20are heated to 800° C. (see steps S6 and S6A), while the presentembodiment is not limited to such a specific example and it is alsopossible to hold the base body 5A inside the melt mixture 290 containingtherein the metal Na and the metal Ga in the step S6A when the reactionvessel 10 and the outer reaction vessel 20 are heated to 800° C. (seestep S6). Thus, when the reaction vessel 10 and the outer reactionvessel 20 are heated to 800° C., it is possible to carry out the crystalgrowth of the GaN crystal from the base body 5A by dipping the base body5A into the melt mixture 290.

It should be noted that the operation for making the base body 5A tocontact with the melt mixture 290 comprises: the step A for applying avibration to the support unit 210 by the vibration application unit 230and detecting the vibration detection signal BDS indicative of thevibration of the support unit 210; and the step B of moving the supportunit 50 by the up/down mechanism 220 such that the vibration detectionsignal changes to the state (component SS2 of the vibration detectionsignal BDS) corresponding to the situation where the base body 5A hasmade contact with the melt mixture 290.

Further, it should be noted that the operation for holding the base body5A in the melt mixture 290 comprises: the step A for applying avibration to the support unit 210 by the vibration application unit 230and detecting the vibration detection signal BDS indicative of thevibration of the support unit 210; and the step B of moving the supportunit 210 by the up/down mechanism 220 such that the vibration detectionsignal changes to the state (component SS3 of the vibration detectionsignal BDS) corresponding to the situation where the base body 5A isdipped into the melt mixture 290.

In the steps B and C, it should be noted that the support unit 210 ismoved by the up/down mechanism 220 because there is caused variation oflocation for the melt surface (=interface 3) for the melt mixture 290formed in the reaction vessel 10 depending on the volume of the reactionvessel 10 and the total amount of the metal Na and the metal Ga loadedinto the reaction vessel 10, as in the case of base body 5A being dippedinto the melt mixture 290 at the moment when the melt mixture 290 isformed in the reaction vessel 10 or as in the case of the base body 5Abeing held in the space 23 and thus there is a need of moving the basebody 5A up or down in the gravitational direction DR1 in order that thebase body 5A makes a contact with the melt mixture 290 or the base body5A is dipped into the melt mixture 290.

Further, while explanation has been made with the step S9A of theflowchart shown in FIG. 20 that the base body 5A is lowered such thatthe base body 5A makes a contact with the melt mixture 290, it should benoted that the step S9A of the present invention shown in the flowchartof FIG. 20 generally comprises a step D that moves the support unit 210by the up/down mechanism 220 such that the GAN crystal grown from thebase body 5A makes a contact with the melt mixture 290 during the growthof the GaN crystal.

It should be noted that, while there occurs lowering of the liquidsurface (=interface 3) of the melt mixture 290 because of consumption ofGa in the melt mixture 290 with progress of growth of the GaN crystal,there may be a case in which it is necessary to move the GaN crystalgrown from base body 5A in the upward direction or in the downwarddirection with the progress of growth of the GaN crystal, depending onthe relationship between the rate of lowering the liquid surface(=interface 3) and the growth rate of the GaN crystal.

Thus, in the case the rate of lowering of the liquid surface (=interface3) is faster than the growth rate of the GaN crystal, the GaN crystalgrown from the base body 5A is moved downward for maintaining thecontact of the GaN crystal with the liquid surface (=interface 3) of themelt mixture 290. On the other hand, in the case the rate of lowering ofthe liquid surface (=interface 3) is slower than the growth rate of theGaN crystal, the GaN crystal grown from the base body 5A is moved upwardfor maintaining the contact of the GaN crystal with the liquid surface(=interface 3) of the melt mixture 290.

Thus, in view of the need of moving the GaN crystal grown from the seedcrystal 5 up or down in the gravitational direction DR1 depending on therelationship between the lowering rate of the liquid surface (=interface3), the step D is defined as “moving the support unit 210 by the up/downmechanism 220”.

Further, it should be noted that the operation for making the GaNcrystal grown from the base body 5A to contact with the melt mixture 290comprises the step A and the step B noted above.

FIG. 21 is a schematic diagram showing the state inside the reactionvessel 10 and the outer reaction vessel 20 in the steps S7 and S9 shownin FIG. 20. Referring to FIG. 21, the temperatures of the reactionvessel 10 and the outer reaction vessel 20 are held at 800° C. duringthe interval from the timing t2 to the timing t6, and growth of the GaNcrystal proceeds in the melt mixture 290. Further, with progress ofgrowth of the GaN crystal, there occurs evaporation of metal Na from themetal melt 190 and the melt mixture 290, and thus, there exist a mixtureof the nitrogen gas 4 and the metal Na vapor 7 in the space 23.

Further, with consumption of the nitrogen gas 4, the pressure P1 of thespace 23 is lowered than the pressure P2 of the space 31 inside theconduit 30.

Then the nitrogen gas is supplied from the space 31 of the conduit 30 tothe metal melt 190 via the stopper/inlet plug 50, wherein the nitrogengas moves through the metal melt 190 in the form of bubbles 191. Thus,the nitrogen gas is supplied to the space 23 through the vapor-liquidinterface 1. Now, when the pressure P1 of the space 23 becomes generallyequal to the pressure P2 inside the space 31, the supply of the nitrogengas from the space 30 of the conduit 31 to the reaction vessel 50 andthe outer reaction vessel 10 via the stopper/inlet plug 20 and the metalmelt 190 is stopped.

Further, the crystal growth apparatus 100 has the feature of growing theGaN crystal in the state in which the metal Na vapor 23 is confined inthe space 5023. In the state the metal Na vapor 7 is confined in thespace 23, the vapor pressure of the metal Na evaporated from the metalmelt 190 becomes generally identical to the vapor pressure of the metalNa evaporated from the melt mixture 290. Thus, with the foregoingfeature, it becomes possible to suppress the variation of mole ratiobetween the metal Na and the metal Ga in the melt mixture 290 caused bythe migration of metal Na from the metal melt 190 to the melt mixture290 or by the migration of metal Na from the melt mixture 290 to themelt mixture 190. As a result, it becomes possible to grow a large,high-quality GaN crystal.

FIG. 22 is a schematic diagram showing the state inside the reactionvessel 10 and the outer reaction vessel 20 in the step S9A shown in FIG.20. It can be seen that there is caused lowering of the vapor-liquidinterface 3 with progress of the growth of the GaN crystal and the GaNcrystal 6 grown from the base body 5A separates from the melt mixture290.

When this occurs, the vibration detection signal BDS becomes solely fromthe component SS1 (see FIG. 18), and thus, the up/down mechanism 220lowers the support unit 210 in response to the vibration detectionsignal BDS such that the GaN crystal 6 makes a contact with the meltmixture 290 according to the process explained above. Thereby, the GaNcrystal contacts with the metal mixture 290 again, and there occurs thepreferential growth the GaN crystal 6.

Thus, with Embodiment 2, the base body 5A or the GaN crystal 6 grownfrom the base body 5A is made contact with the melt mixture 290constantly during the growth of the GaN crystal.

With this, it becomes possible to grow a GaN crystal of large size.

Further, while the present embodiment has been explained for the case inwhich the support unit 210 is applied with vibration and the base body5A or the GaN crystal 6 is controlled to make a contact with the meltmixture 290 while detecting the vibration of the support unit 210, thepresent embodiment is not limited to such a construction and it is alsopossible to cause the base body 5A or the GaN crystal 6 to make acontact with the melt mixture 290 by detecting the location of thevapor-liquid interface 3. In this case, an end of a conductor wire isconnected to the outer reaction vessel 20 from the outside and the otherend is dipped into the melt mixture 290. Further, an electric current iscaused to flow through the conductor wire in this state and location ofthe vapor-liquid interface 3 is detected in terms of the length of theconductor wire in the outer reaction vessel 20 in which there has beennoted a change of the current from Off to On.

Thus, when the other end of the conductor wire is dipped into the meltmixture 290, there is caused conduction of the current through the meltmixture 290, the reaction vessel 10, the metal melt 190 and the outerreaction vessel 20, while when the other end is not dipped into the meltmixture 290, no current flows through the conductor wire.

Thus, it is possible to detect the location of the vapor-liquidinterface 20 by the length of the conductor wire inserted into the outerreaction vessel 3 for the case of causing the change of state of theelectric current from Off to On. When the location of the vapor-liquidinterface 3 is detected, the up/down mechanism 220 lowers the base body5A or the GaN crystal 6 to the location of the detected vapor-liquidinterface 3.

Further, it is also possible to detect the location of the vapor-liquidinterface 3 by emitting a sound to the vapor-liquid interface 3 andmeasuring the time for the sound to go and back to and from thevapor-liquid interface 3.

Further, it is possible to insert a thermocouple into the reactionvessel 20 from the outer reaction vessel 10 and detect the location ofthe vapor-liquid interface 20 from the length of the thermocoupleinserted into the outer reaction vessel 3 at the moment when thedetected temperature has been changed.

In the foregoing, explanation has been made that the crystal growth ofthe GaN crystal 550 of reduced threading dislocations is made by causingthe base body 5A to make a contact with the surface of the melt mixture290 (=interface 3) by using the support unit 210, the present inventionis not limited to such a construction and it is also possible to achievethe crystal growth of the GaN crystal 550 of reduced threadingdislocations by causing the base body 5, 5B or 5C to make a contact withthe surface of the melt mixture 290 (=interface 3) in place of the basebody 5A by using the support unit 210.

In the case of using the base body 5 or 5C, the support unit 210 isformed by a hollow cylindrical member and form plural apertures at thetip end part of the hollow cylindrical member. The base body 5 or 5C isthereby supported by vacuum chuck by evacuating the interior of thehollow cylindrical member.

Further, while it has been described in the foregoing that the base body5A is moved up or down depending on the relationship between the crystalgrowth rate of the GaN crystal and the lowering rate of the interface 3for maintaining contact of the base body 5A with the interface 3, it isalso possible to move the support unit 210 up or down by the up/downmechanism 220 so as to maintain the contact of the GaN crystal 6 withthe interface 3, by taking into consideration the effect of rising ofthe interface 3 caused by dipping of the GaN crystal 6 grown from thebase body 5A into the melt mixture 290 and the effect of the lowering ofthe interface caused by the upward movement of the GaN crystal 6 fromthe melt mixture 290.

In the case the temperature of the metal melt 190 is equal to thetemperature of the melt mixture 290, the vapor pressure of the metal Naevaporated from the metal melt 190 becomes higher than the vaporpressure of the metal Na evaporated from the melt mixture 290. Thus, insuch a case, the metal Na migrates from the metal melt 190 to the meltmixture 290 and there is caused rising of the interface 3. Thus, in theevent the temperature of the metal melt 190 and the temperature of themelt mixture 290 are set equal, it is possible to move the support unit210 up or down by the up/down mechanism 220 such that the GaN crystal 6makes a contact with the interface 3 while taking into consideration ofthe effect of rising of the interface 3 caused by the migration of themetal Na from the metal melt 190 to the melt mixture 290.

Further, with growth of the GaN crystal 6, the metal Ga in the meltmixture 290 is consumed while this consumption of the metal Ga inviteslowering of the interface 3. Thus, it is also possible to move thesupport unit 210 up or down by the up/down mechanism 220 such that theGaN crystal 6 makes a contact with the interface 3 while taking intoconsideration the amount of consumption of the metal Ga.

Otherwise, the present embodiment is identical to Embodiment 1.

Embodiment 3

FIG. 23 is a schematic cross-sectional diagram showing a crystal growthapparatus according to Embodiment 3 of the present invention. Referringto FIG. 23, a crystal growth apparatus 100B of Embodiment 3 has aconstruction generally identical with the construction of the crystalgrowth apparatus 100 shown in FIG. 1, except that the conduit 40 and theheating unit 80 are removed.

With the crystal growth apparatus 100B, the reaction vessel 10 holds amelt mixture 320 in place of the melt mixture 290. The melt mixture 320comprises a melt mixture of metal Na and metal Ga.

FIG. 24 is a timing chart showing the temperature of the reaction vessel10 and the outer reaction vessel 20 and a Li concentration in the meltmixture 320. Referring to FIG. 24, the temperatures of the reactionvessel 10 and the outer reaction vessel 20 are elevated in the crystalgrowth apparatus 100B along the curve k2 and are held at 800° C.similarly to the crystal growth apparatus 100.

The curve k4 represents the Li concentration in the melt mixture 320.

It can be seen that the Li concentration increases with a constant ratein the interval from the timing t2 to the timing t6. In the presentcase, the Li concentration becomes 0.5 mol % at the timing t3 and 0.8mol % at the timing t6.

As explained in Embodiment 1, there occurs a crystal growth of a GaNcrystal having a dimple surface, and thus the GaN crystal 530 having theoblique faces, in the case the Li concentration in the melt mixture 320is lower than the range of 0.5-0.8 mol %. On the other hand, in the casethe Li concentration in the melt mixture 320 is in the rage of 0.5-0.8mol %, there takes place the crystal growth of a GaN crystal having agenerally flat surface.

Thus, the present embodiment forms the GaN crystal 430 having theoblique facets on the base body 5 during the interval from the timing t2to the timing t3 and forms the GaN crystal 550 of generally flat surfaceon the GaN crystal 530 during the interval from the timing t3 to thetiming t6.

With progress of the crystal growth of the GaN crystals 530 and 550, themetal Ga in the melt mixture 320 is decreased, and as a result, the Liconcentration in the melt mixture 320 increases with a constant rateshown by the curve k4 during the interval from the timing t2 to thetiming t6.

In order to set the Li concentration to be equal to or lower than 0.5mol % at the timing t2 in which the crystal growth of the GaN crystal530 on the base body 5 is started, it is sufficient to load the metal Lawith an amount smaller than the Li amount of 2.2 mg shown in Table 1 inthe reaction vessel 10 together with the metal Na and metal Ga in theglove box.

FIG. 25 is a flowchart explaining the manufacturing method of a GaNcrystal according to Embodiment 3 of the present invention. It should benoted that the flowchart of FIG. 25 is identical to the flowchart shownin FIG. 11 except that the step S2 of the flowchart shown in FIG. 11 isreplaced with a step S2A and the steps S4 and S8 are deleted.

Referring to FIG. 25, the metal Ga and metal Li are loaded into thereaction vessel 10 in the Ar gas ambient after the step S1 noted above(step S2A). Thereafter, the steps S3 and S5-S7, S9 and S10 are executedconsecutively, and the GaN crystals 530 and 550 are formed on the basebody 5 consecutively.

In this case, the step S7 is executed during the interval from thetiming t2 to the timing t3 shown in FIG. 24, and the step S9 is executedduring the interval from the timing t3 to the timing t6 showing in FIG.24.

FIG. 26 is another schematic cross-sectional diagram showing a crystalgrowth apparatus according to Embodiment 3 of the present invention. Itshould be noted that the crystal growth apparatus of Embodiment 3 may bethe crystal growth apparatus 100C shown in FIG. 26. Referring to FIG.26, the crystal growth apparatus 100C has a construction generallyidentical with the construction of the crystal growth apparatus 100A,except that the conduit 40 and the heating unit 80 are removed from thecrystal growth apparatus 100A shown in FIG. 15.

With the crystal growth apparatus 100C the reaction vessel 10 holds amelt mixture 320 in place of the melt mixture 290 similarly to thecrystal growth apparatus 100B.

Thus, the crystal growth apparatus 100C changes the Li concentration inthe melt mixture 320 along the curve k4 during the interval from thetiming t2 to the timing t6 shown in FIG. 24, and the GaN crystals 530and 550 are grown consecutively from the seed crystal 5A.

FIG. 27 is another flowchart explaining the manufacturing method of aGaN crystal according to Embodiment 3 of the present invention. Itshould be noted that the flowchart of FIG. 27 is identical to theflowchart shown in FIG. 20 except that the step S2 of the flowchartshown in FIG. 20 is replaced with a step S2A and the steps S4 and S8 aredeleted.

Referring to FIG. 27, the metal Ga and metal Li are loaded into thereaction vessel 10 in the Ar gas ambient after the step S1 noted above(step S2A). Thereafter, the steps S3, S5, S6, S6A, S7, S9, S9A and S10are executed consecutively, and the GaN crystals 530 and 550 are formedon the base body 5 consecutively.

In this case, too, the step S7 is executed during the interval from thetiming t2 to the timing t3 shown in FIG. 24, and the step S9 is executedduring the interval from the timing t3 to the timing t6 showing in FIG.24.

Thus, it is possible to manufacture a GaN crystal of reduced dislocationdensity also by the method of loading the metal Na, metal Ga and metalLi into the reaction vessel 10 in the glove box, by deflecting thethreading dislocations in the direction different from the crystalgrowth direction from the base body 5.

Otherwise, the present embodiment is identical to Embodiment 1 orEmbodiment 2.

FIG. 28 is another oblique view diagram of the stopper/inlet plugaccording to the present invention. Further, FIG. 29 is across-sectional diagram showing the method for mounting thestopper/inlet plug 400 shown in FIG. 28. Referring to FIG. 28, thestopper/inlet plug 400 comprises a plug 401 and a plurality ofprojections 402. The plug 401 is formed of a cylindrical body thatchanges the diameter in a length direction DR3. Each of the projections402 has a generally semispherical shape of the diameter of several tenmicrons. The projections 402 are formed on an outer peripheral surface401A of the plug 401 in a random pattern. Thereby, the separationbetween adjacent two projections 402 is set to several ten microns.

Referring to FIG. 29, the stopper/inlet plug 400 is fixed to aconnection part of the outer reaction vessel 20 and the conduit 30 bysupport members 403 and 404. More specifically, the stopper/inlet plug400 is fixed by being sandwiched between the support member 403 havingone end fixed upon the outer reaction vessel 20 and the support member404 having one end fixed upon an inner wall surface of the conduit 30.

In the present case, the projections 400 of the stopper/inlet plug 402may or may not contact with the outer reaction vessel 20 or the conduit30. In the event the stopper/inlet plug 402 is fixed in the state inwhich the projections 400 do not contact with the outer reaction vessel20 and the conduit 30, the separation between the projections 402 andthe reaction vessel 20 or the separation between the projections 400 andthe conduit 30 is set such that the metal melt 190 can be held by thesurface tension thereof, and the stopper/inlet plug 403 is fixed in thisstate by the support members 404 and 4404.

The metal Na held between the reaction vessel 10 and the outer reactionvessel 20 takes a solid form before heating of the reaction vessel 10and the outer reaction vessel 20 is commenced, and thus, the nitrogengas supplied from the gas cylinder 140 can cause diffusion between thespace 20 inside the outer reaction vessel 23 and the space 30 inside theconduit 31 through the stopper/inlet plug 400.

When heating of the reaction vessel 10 and the outer reaction vessel 20is started and the temperatures of the reaction vessel 10 and the outerreaction vessel 20 are elevated to 98° C. or higher, the metal Na heldbetween the reaction vessel 10 and the outer reaction vessel 20undergoes melting to form the metal melt 190, while the metal melt 190thus formed functions to confine the nitrogen gas into the space 23.

Further, the stopper/inlet plug 400 holds the metal melt 190 by thesurface tension thereof such that the metal melt 190 does not flow outfrom the interior of the outer reaction vessel 20 to the space 30 of theconduit 31.

Further, with progress of the growth of the GaN crystal, the metal melt190 and the stopper/inlet plug 400 confine the nitrogen gas and themetal Na vapor evaporated from the metal melt 190 and the melt mixture290 into the space 23. As a result, the variation of mole ratio of themetal Na and metal Ga in the melt mixture 290 caused by the migration ofthe metal Na from the metal melt 190 to the melt mixture 290 and themigration of metal Na from the melt mixture 290 to the metal melt 190 issuppressed. Further, when there is caused a decrease of nitrogen gas inthe space 23 with progress of growth of the GaN crystal, the pressure P1of the space 23 becomes lower than the pressure P2 of the space 30inside the conduit 31, and the stopper/inlet plug 400 supplies thenitrogen gas to the space 31 via the metal melt 190 by causing to flowthe nitrogen gas therethrough in the direction toward the outer reactionvessel 20.

Thus, the stopper/inlet plug 400 functions similarly to thestopper/inlet plug 50 explained before. Thus, the stopper/inlet plug 400can be used in the crystal growth apparatuses 100, 100A, 100B and 100Cin place of the stopper/inlet plug 50.

While it has been explained that the stopper/inlet plug 400 has theprojections 402, it is also possible that the stopper/inlet plug 400does not have the projections 402. In this case, the stopper/inlet plug400 is fixed by the support members such that the separation between theplug 401 and the reaction vessel 20 or the separation between the plug401 and the conduit 30 becomes several ten microns.

Further, it is also possible to set the separation between thestopper/inlet plug 400 (including both of the cases in which thestopper/inlet plug 402 carries the projections 402 and the case in whichthe stopper/inlet plug 400 does not carry the projections 402) and theouter reaction vessel 20 and between the stopper/inlet plug 400 and theconduit 30 according to the temperature of the stopper/inlet plug 400.In this case, the separation between the stopper/inlet plug 400 and thereaction vessel 20 or the separation between the stopper/inlet plug 400and the conduit 30 is set relatively narrow when the temperature of thestopper/inlet plug 400 is relatively high. When the temperature of thestopper/inlet plug 400 is relatively low, on the other hand, theseparation between the stopper/inlet plug 400 and the reaction vessel 20or the separation between the stopper/inlet plug 400 and the conduit 30is set relatively large.

It should be noted that the separation between the stopper/inlet plug400 and the reaction vessel 20 or the separation between thestopper/inlet plug 400 and the conduit 30 that can hold the metal melt190 changes depending on the temperature of the stopper/inlet plug 400.This, with this embodiment, the separation between the stopper/inletplug 400 and the reaction vessel 20 or the separation between thestopper/inlet plug 400 and the conduit 30 is changed in response to thetemperature of the stopper/inlet plug 400 such that the metal melt 190is held securely by the surface tension.

The temperature control of the stopper/inlet valve 400 is achieved bythe heating unit 70. Thus, when the stopper/inlet plug 400 is to beheated to a temperature higher than 150° C., the stopper/inlet plug 400is heated by the heating unit 70.

FIG. 30 is a further oblique view diagram of the stopper/inlet plugaccording to the present invention. Referring to FIG. 30, thestopper/inlet plug 410 comprises a plug 411 formed with a plurality ofpenetrating holes 412. The plurality of penetrating holes 412 are formedin the length direction DR2 of the plug 411. Further, each of the pluralpenetrating holes 412 has a diameter of several ten microns (see FIG.30A).

With the stopper/inlet plug 410, it is sufficient that there is formedat least one penetrating hole 412.

Further, the stopper/inlet plug 420 comprises a plug 421 formed withplural penetrating holes 422. The plurality of penetrating holes 422 areformed in the length direction DR2 of the plug 421. Each of thepenetrating holes 422 have a diameter that changes stepwise from adiameter r1, r2 and r3 in the length direction DR2. Here, each of thediameters r1, r2 and r3 is determined in the range such as severalmicrons to several ten microns in which the metal melt 190 can be heldby the surface tension Reference should be made to FIG. 30B.

With the stopper/inlet plug 420, it is sufficient that there is formedat least one penetrating hole 422. Further, it is sufficient that thediameter of the penetrating hole 422 is changed at least in two steps.Alternatively, the diameter of the penetrating hole 422 may be changedcontinuously in the length direction DR2.

The stopper/inlet plug 410 or 420 can be used in any of the crystalgrowth apparatuses 100, 100A 100B and 100C in place of the stopper/inletplug 50.

In the case the stopper/inlet plug 420 is used in the crystal growthapparatus 100, 100A, 100B or 100C in place of the stopper/inlet plug 50,it becomes possible to hold the metal melt 190 by the surface tensionthereof by one of the plural diameters that are changed stepwise withoutconducting precise temperature control, and it becomes possible tomanufacture a GaN crystal of large size without conducting precisetemperature control of the stopper/inlet plug 420.

Further, with the present invention, it is possible to use a porous plugor check valve in place of the stopper/inlet plug 50. The porous plugmay be the one formed of a sintered body of stainless steel powders.Such a porous plug has a structure in which there are formed a largenumber of pores of several ten microns. Thus, the porous plug can holdthe metal melt 190 by the surface tension thereof similarly to thestopper/inlet plug 60 explained before.

Further, the check valve of the present invention may include both aspring-actuated check valve used for low temperature regions and apiston-actuated check valve used for high temperature regions. Thispiston-actuated check valve is a check valve of the type in which apiston guided by a pair of guide members is moved in the upwarddirection by the differential pressure between the pressure P2 of thespace 31 and the pressure P1 of the space 23 for allowing the nitrogengas in the space 31 to the space 23 through the metal melt 190 in theevent the pressure P2 is higher than the pressure P1 and blocks theconnection between the outer reaction vessel 20 and the conduit 30 bythe self gravity when P1≧P2. Thus, this check valve can be used also inthe high-temperature region.

While explanation has been made with Embodiments 1-3 that the GaNcrystal 550 of reduced threading dislocations is manufactured by growingGaN crystals on any of the base bodies 5, 5A, 5B and 5C consecutivelyunder that condition where the oblique facets are formed and then underthe condition that a flat surface is formed, the present invention isnot limited to such specific examples, and any process may be employedin general as long as it is possible to manufacture a GaN crystal ofreduced threading dislocations under the condition of deflecting thethreading dislocations in the direction different from the crystalgrowth direction from the base body and then under the condition inwhich the condition in which the surface of the GaN crystal forms agenerally perpendicular plane with regard to the growth direction fromthe base body.

Further, while it has been explained with Embodiments 1-3 that thecrystal growth temperature is 800° C., the present embodiment is notlimited to this specific crystal growth temperature. It is sufficientwhen the crystal growth temperature is equal to or higher than 600° withthe present invention. Further, it is sufficient that the nitrogen gaspressure may be any pressure as long as crystal growth of the presentinvention is possible under the pressurized state of 0.4 MPa or higher.Thus, the upper limit of the nitrogen gas pressure is not limited to5.05 MPa but a pressure of 5.05 MPa or higher may also be used.

Further, while explanation has been made in the foregoing that metal Naand metal Ga are loaded into the reaction vessel 10 in the ambient of Argas and the metal Na is loaded between the reaction vessel 10 and theouter reaction vessel 20 in the ambient of Ar gas, it is also possibleto load the metal Na and the metal Ga into the reaction vessel 10 andthe metal Na between the reaction vessel 10 and the outer reactionvessel 20 and load the metal Li and metal Ga into the conduit 40 in theambient of a gas other than the Ar gas, such as He, Ne, Kr, or the like,or in a nitrogen gas. Generally speaking, the metal Na and the metal Gaare loaded into the reaction vessel 10 and the metal Na is loadedbetween the reaction vessel 10 and the outer reaction vessel 20 and themetal Li and metal Ga into the conduit 40 in the ambient of an inert gasor nitrogen gas. In this case, the inert gas or the nitrogen gas shouldhave the water content of 10 ppm or less and the oxygen content of 10ppm or less.

Further, while explanation has been made in the foregoing that the metalthat is mixed with the metal Ga is Na, the present embodiment is notlimited to this particular case, but it is also possible to form themelt mixture 290 by mixing an alkali metal such as potassium (K), or thelike, or an alkali earth metal such as magnesium (Mg), calcium (Ca),strontium (Sr), or the like, with the metal Ga. Thereby, it should benoted that the melt of the alkali metal forms an alkali metal melt whilethe melt of the alkali earth melt forms an alkali earth metal melt .

Further, in place of the nitrogen gas, it is also possible to use acompound containing therein nitrogen as a constituent element such assodium azide, ammonia, or the like. These compounds constitute thenitrogen source gas.

Further, place of Ga, it is also possible to use a group III metal suchas boron (B), aluminum (Al), indium (In), or the like.

Thus, the crystal growth method of the present invention is generallyapplicable to the manufacturing of a group III nitride crystal whileusing a melt mixture of an alkali metal or an alkali earth melt and agroup III metal (including boron).

The group III nitride crystal manufactured with the crystal growthmethod of the present invention may be used for fabrication of group IIInitride semiconductor devices including light-emitting diodes, laserdiodes, photodiodes, transistors, and the like.

Further, in the present invention, it should be noted that “group III”means “group IIIB” as defined in a periodic table of IUPAC(International Union of Pure and Applied Chemistry).

Further, it should be noted that the embodiments explained above areprovided merely for the purpose of showing examples and should not beinterpreted that the present invention is limited to such specificembodiments. The present invention is not limited to the embodimentsdescribed heretofore, but various variations and modifications may bemade without departing from the scope of the invention as set forth inpatent claims.

The present invention is applied to a group III nitride crystal ofreduced threading dislocations manufactured by the crystal growth methodthat uses an alkali metal as the flux. Further, the present invention isapplied to the manufacturing method of a group III nitride crystal thatmanufactures the group III nitride crystal of reduced threadingdislocations by using an alkali metal for the flux.

The present invention is based on Japanese priority application2005-335684 filed on Nov. 21, 2005, the entire contents of which areincorporated hereby as reference.

1. A group III nitride crystal containing therein an alkali metal element, comprising: a base body; a first group III nitride crystal formed such that at least a part thereof makes a contact with said base body, said first group III nitride crystal deflecting threading dislocations in a direction different from a direction of crystal growth from said base body; and a second nitride crystal formed adjacent to said first group III nitride crystal, said second nitride crystal having a crystal growth surface generally perpendicular to said direction of the crystal growth.
 2. The group III nitride crystal as claimed in claim 1, wherein said first group III nitride crystal has a crystal growth surface different from a c-surface and a plane parallel to a c-axis.
 3. The nitride crystal as claimed in claim 1, wherein said second group III nitride crystal has a crystal growth direction in said c-axis.
 4. The crystal growth apparatus as claimed in claim 1, wherein said base body comprises a substrate of a material other than said group III nitride crystal.
 5. The group III nitride crystal as claimed in claim 1, wherein said base body comprises a substrate of a material different from said group III nitride crystal, and a third group III nitride crystal formed on said substrate, said third group III nitride crystal containing threading dislocations, said first group III nitride crystal being formed such that at least a part thereof is in contact with said third group III nitride crystal.
 6. The group III nitride crystal as claimed in claim 5, wherein said third group III nitride crystal comprises plural crystals disposed with a predetermined interval.
 7. The group III nitride crystal as claimed in claim 6, wherein said predetermined interval is determined according to a size of a semiconductor device fabricated by using said second group III nitride crystal.
 8. The group III nitride crystal as claimed in claim 1, wherein said base body comprises a group III nitride crystal.
 9. The group III nitride crystal as claimed in claim 1, wherein said base body comprises a substrate of a seed crystal formed of a group III nitride crystal, and a third group III nitride crystal formed adjacent to said seed crystal, said third group III nitride crystal containing threading dislocations, said first group III nitride crystal being formed such that at least a part thereof is in contact with said third group III nitride crystal.
 10. The group III nitride crystal as claimed in claim 5, wherein said third group III nitride crystal contains therein threading dislocations with a density of 10⁶-10¹⁰ cm⁻².
 11. A method for manufacturing a group III nitride crystal on a base body by using a crystal growth apparatus, said crystal growth apparatus comprising a reaction vessel holding a melt mixture of an alkali metal and a group III metal, said method comprising: a first step of loading said alkali metal and said group III metal into said reaction vessel in an inert gas ambient or a nitrogen gas ambient; a second step of filling said vessel space of said reaction vessel with a nitrogen source gas; a third step of heating said reaction vessel to a crystal growth temperature; a fourth step of growing a first group III nitride crystal on said base body, such that said first group III nitride crystal deflects threading dislocations in a direction different from a crystal growth direction from said base body; a fifth step of growing a second group III nitride crystal having a crystal growth surface generally perpendicular to said crystal growth direction such that at least a part of said second group III nitride crystal makes a contact with said first group III nitride crystal; and a sixth step of supplying said nitrogen source gas to said reaction vessel such that a pressure inside said vessel space is maintained to a predetermined pressure.
 12. The manufacturing method as claimed in claim 11, wherein said fourth step causes crystal growth of said first group III nitride crystal such that said first group III nitride crystal has a crystal growth surface different from a c-surface or a plane parallel to a c-axis.
 13. The method as claimed in claim 12, wherein said fourth step causes crystal growth of said first group III nitride crystal by controlling a mixing ratio of said alkali metal and said group III metal and a nitrogen source gas pressure in said vessel space within a range of crystal growth condition in which there occurs no new nucleation in said melt mixture.
 14. The method as claimed in claim 13, wherein said fourth step causes said crystal growth of said first group III nitride crystal by relatively lowering said nitrogen source gas pressure when said mixing ratio is relatively large and causes said crystal growth of said first group III nitride by relatively increasing said nitrogen source gas pressure when said mixing ratio is relatively small.
 15. The method as claimed in claim 11, wherein said fifth step causes said crystal growth of said second group III nitride crystal by adding an additive different from any of said alkali metal and said group III metal to said melt mixture.
 16. The method as claimed in claim 15, wherein said fifth step causes said crystal growth of said second group III nitride crystal under a crystal growth condition for causing crystal growth of said first group III nitride crystal while adding said additive to said melt mixture.
 17. The method as claimed in claim 16, wherein said alkali metal comprises sodium, said group III metal comprises gallium, and said additive comprises lithium.
 18. The method as claimed in claim 17, wherein said lithium is used in said melt mixture of sodium and gallium with a concentration of 0.5-0.8 mol %.
 19. The method as claimed in claim 11, further comprises a seventh step of dipping said base body into said melt mixture.
 20. The method as claimed in claim 11, further comprising a seventh step of causing said base body to make a contact with a vapor-liquid interface between said melt mixture and said vessel space.
 21. The method as claimed in claim 20, wherein said manufacturing method further comprises an eighth step of moving said base body with a growth of said first and second group III nitride crystal such that said crystal growth surface maintains a contact with said vapor-liquid interface.
 22. The method as claimed in claim 11, wherein said base body comprises a substrate of a material other than said group III nitride crystal.
 23. The method as claimed in claim 11, wherein said base body comprises a substrate of a material different from said group III nitride crystal and a third group III nitride crystal formed on said substrate, said third group III nitride crystal containing threading dislocations, said fourth step of said manufacturing method being conducted such that said first group III nitride crystal is grown in contact with said third group III nitride crystal.
 24. The method as claimed in claim 23, wherein said third group III nitride comprises plural crystals each having a predetermined width and disposed with a predetermined interval.
 25. The method as claimed in claim 11, wherein said base body comprises a group III nitride crystal of a low-grade crystal having threading dislocations.
 26. The method as claimed in claim 11, wherein said base body comprises a seed crystal of a group III nitride crystal and a third group III nitride crystal formed adjacent to said seed crystal, said third group III nitride crystal containing threading dislocations therein, said fourth step of said manufacturing method being conducted such that said first group III nitride crystal is grown in contact with said third group III nitride crystal. 